DE2024047A1 - Polyazo dyes, their metal complex compounds, their production and use - Google Patents

Description

Polyazo dyes, their metal complex compounds, their manufacture and use. ■

The purpose of the invention are trisazo dyes and their metal ' 'Complex compounds that have a monoazo dye as the basic structure Made from 'picric acid and resorcinol, for coloring of leather with improved leveling properties.

The invention thus relates to polyazo dyes and their metal complex compounds sovij.e mixtures of such Metallkoiiiploxverbindungen, which in the metal-free form the formula

.BAD ORIGINAL 009848/1826

(D

correspond,

wherein A and A 'stand for an amino or hydroxyl group and X is hydrogen, hydroxyl, halogen, nitro, optionally substituted alkyl or alkoxy or the SuIfons acid group,

Y is hydrogen, hydroxyl, halogen, nitro, optionally substituted alkyl or alkoxy or the group

-NII

where Z is hydrogen, the carboxyl or the sulfonic acid

regruppe,
Z, for hydrogen, hydroxyl, nitro, optionally

substituted alkyl or alkoxy and Zp for hydrogen or nitro.

009848/18 26

BATH

T is the carboxyl or sulfonic acid group, T, hydrogen, nitro, halogen, optionally substituted alkyl or alkoxy or the sulfonic acid group · And Tp hydrogen, nitro, halogen or optionally

substituted alkyl or alkoxy, and rings B and / or D contain a sulfonic acid group ".

The new polyazo dyes and their metal complex compounds genes can be obtained by converting 1 mole of a diazo compound from an amine of the formula

) (II)

with 1 mole of a coupling component of the formula

OH

NO,

A '

(III)

to the disazo dyes of the formula

OH A

NO,

A ¹

009848/1826

(IV)

couples and this with a diazo compound from an amine the formula

(V)

reacts, and the dyes obtained in this way, optionally with treated metal-donating agents in such a way that metal-containing trisazo dyes are formed.

Good dyes and their metal complex compounds correspond to the formula in the metal-free form

OH

OH

T,

(VI)

Similarly good dyes and their metal complex compounds correspond to the formula in the metal-free form

OH

OH

S0, H

Oo

9 048/182 ^

wherein R is hydrogen, halogen, nitro or low molecular weight alkyl or alkoxy, R ₁ -SOJl or -COOK and R _{0 is} hydrogen, halogen, nitro or low molecular weight

res denote alkyl or alkoxy or of the formula

(VIII),

wherein R ₁ ~ SO., H or -COOH and R-, mean single-molecular alkoxy.

Equally good dyes and their metal complex compounds correspond in the metal-free form, the formula.

OH

• where R "SO ₇ II or -COOH,

0098 48/1026

202-047

R is hydrogen, halogen, nitro or low molecular weight

Alkyl or alkoxy,
R, hydrogen, nitro or -COOH

and R. are hydrogen or nitro or of the formula 0

OH OH SOY

NH-

> Λ) Η ϋ _(χ)

N = N- / "Λ ^R l

wherein R is -SO, H or -COOH. '

Compared to the closest comparable known from Swiss patent specification No. 444996, possibly containing metal Dyes, the optionally metal-containing dyes produced according to the invention are distinguished Formula (I) due to better solubility in water, better leveling ability on grain leather and better migration in polyvinyl chloride and raw rubber.

For the production of such Metallkomploxverbiridungen can in;; special lh ·; Chromium, copper, nickel, mangle, cobalt odor iron compounds in particular have been used.

9048/1826

The metal-containing dyes of the formula (I) can be but also produce if you have a metal-containing, preferably a copper, nickel, chrome, manganese,! cobalt or ferruginous coupling components that are in the metal-free state corresponds to the formula (IJl).

The metallization of the compounds of formula (I) or (131) is advantageously used in an aqueous medium, if appropriate with the addition of an organic solvent or then in carried out in an organic solvent alone.

The metallization is advantageously carried out in such a way that on two equivalents azo compounds one less act as two, but at least one equivalent metal-containing amount of a metal donor leaves. 1: 2 metal complex compounds are preferably obtained from the dyes of the formula (3). When metallizing mixtures, two of the same can be found or at least two different azo compounds of the formula (I) *. So so-called homogeneous, uniform or symmetrical or heterogeneous, mixed or asymmetrical 1: 2 metal complexes obtained will. ·

It is advantageous to work in an acidic medium; but can

008848/1826

Metallization can optionally also be carried out in a neutral to alkaline medium.

Suitable copper compounds are e.g. cupric sulfate, cupriformate, Cupric acetate or cupric chloride.

Nickel formate, Nickelace · "-tat. And nickel ^sulphates: /...f·! ■, - · i:. -. '. ··.;

Suitable compounds of chromium are e.g. chromium trioxide, Chromifluoridj, Chromisulfat, Chroroiformiat, Chromiacetat, ν Potash urachromisulphate or ammonium chromisulphate. Also the chromates, e.g. sodium or potassium chromate or -bichromate, are ideally suited for metallization.

Manganese, cobalt or, for example, serve as manganese, cobalt or iron compounds. Eisehformiät, -aetät and -sulfat /. " ^:

PUr iialQeen .tfcfifli. vo «v ^» white «B; chlorine odtip Βία« || ii ¥

benenfalls'substituiertes niedrigmolekulap ·· alkyl txiit · Al:% T '^ -alkoxy eolche radicals having from i to 6, preferably 1 to J ,, Coals "\

material atoms, e.g. methyl, ethyl, Pro ^ yIV Ieopropyl, methoxy,

. ". '■ ■« ^..; \'";·; ·: '·. · ■ ■■. , ν ^; ■ ) ■ , • -i.Av.v-'k '' - '.. .'I' _r ^ ^f ethoxy, gyanethyl, hydroxyethyl ,; ChlormÄth ^ l, ⁵ chlorine ^ tftyir X $ 'r!>;

009848/1826 originally inspected

■ -. 9 -

The optionally metallized compounds of the formula (I) can be obtained if one mole of a coupling component is used of the formula (III) of a diazo compound from an amine of the formula (II) in an alkaline medium at a pH from 7.5 to 12, preferably from 8 to 9, to the disazo dye (TV) couples and this with a diazo compound from an amine of the formula (V) in an acidic medium at a pH of from 3 to 7, preferably from 4.5 to 5.5.

A preferred method is / that you get a mixture from 0.2-0.8 mol, but advantageously 0.5 mol, of a diazo compound and 0.8-0.2 mol, but advantageously 0.5 mol, one of the first diazo compound different from an amine of the formula (II) diazo compound at the same time or

successively with 1 mole of a coupling component of the formula (III) couples to the disazo dye mixture (JVa) and this Dlsazo dye mixture then with a diazo compound from an amine of the formula (V).

The optionally metallized dyes obtained are used for dyeing or printing leather. It can do this

009343/1823

Mixtures of several, optionally metallized, dyes can also be used.

The resulting, optionally metal-containing, dyes are distinguished by very good leveling power, nuance constancy on leathers of different tannings, good dye build-up in neutral to weakly acidic dyebaths, good fastness to sanding on chrome suede, very good fastness to migration on polyvinyl chloride and crepe rubber; very good water, washing, Schwelss- and formaldehyde fastness, very good ironing fastness and very good light fastness _t The dyes build particular leathers lower affinity, for. B, chrome vegetable tanned, chrome synthetic tanned leather, to deep, rich nuances; they also have a high neutral drawability on this material.

In the following examples, the parts mean Gewlohtstelle and the temperatures are given in degrees Celsius.

example 1

199 parts (1 mol) of 1-amine-2-hydroxy-3,5-dinitrobenzene are used in the usual catfish diazotized and in soda ash

009848/1826

■ «■ η -

Solution coupled at a pH of 8 to 9 to 110 parts (1 mol) of 1,3-dihydroxybenzene at a temperature of 10-15 °. 309 parts (l mol) of 4-amino-4'-nitro-2 ¹ -sulf © diphenylamine are diazotized with sodium nitrite in the usual way in the presence of hydrochloric acid and then coupled to the monoazo dye obtained, the pH being between 8 with sodium hydroxide solution and 8.5 and the temperature is kept at 20 °. In the alkaline coupling solution is in the course

from 20 minutes the diazo compound from 218 parts (1 mol), 1-amino-2-sulfo <-4-nitro-benzene, added dropwise, no that the coupling takes place at a pH between 6 and 6.5. After the coupling has ended, the reaction solution is heated to 60 ° and ikh parts of crystallized iron sulfate (0.5 mol) are added and the dye is heated to 95-100 ° for one hour.

After metallization has taken place, the dye is deposited by adding sodium chloride, isolated and dried. When dry, it makes a dark brown fuIver which dissolves in water with a dark yellow-brown color and piping in daisy-yellow-brown tones. Replace the iron sulfate with the appropriate amount a copper, cobalt or chromium releasing agent, ßö receives the corresponding copper, cobalt or chromium complex, all have similar good properties »

009848/1826

Dyeing example A

100 parts of freshly tanned and neutralized chrome grain leather are drummed in a fleet of 250 parts of water at 65 ⁰ and 1 part of the dyestuff prepared according to Example 1 during JO minutes in the dyeing drum, in the same bath with 2 parts of an anionic fatliquor on sulfönierter Tranbasis during Welter en JO Minutes, and the leather is dried and trimmed in the usual way. A leather which is very evenly colored and has a dark brown shade is obtained.

Dyeing example B

100 parts of calfskin suede are drummed up with 1000 parts of water and 2 parts of ammonia in a dyeing drum for 4 hours and then colored in a fresh bath. 500 parts of water at 65 °, 2 parts of ammonia, 10 parts of the dissolved, The dye described under Example 1 are used together with the calf leather that was rolled out beforehand during 1 Dyed in the staining drum for an hour and 20 minutes. To exhaustion of the dyebath slowly add 4 parts of formic acid (85 #) added and colored further until the dye is completely fixed.

The suede leather, rinsed, dried and trimmed in the usual way, is obtained after sanding the suede side a dark brown colored, very even suede.

009848/1826

Dyeing Example C

100 parts lamb leather, chrome-vegetable tanned, 10 parts des

The dye obtained in Example 1 are in a dyeing drum in a liquor of 1000 parts of water at 55 ° and 1.5 parts an anionic spermacet oil emulsion for 45 minutes and the dye by slowly adding 5 parts of formic acid ($ 85) fixed on the leather for 50 minutes. After the usual drying and dressing, a leather in a dark brown shade of good levelness is obtained.

Dyeing example D

A solution of 20 parts of the dye prepared according to Example 1 in 8 ^ 7 parts of water, 150 parts of ethyl glycol and j3 parts of formic acid (85 # ig) is applied to the grain side of a sanded, combined-tanned cowhide leather by spraying, plushing and pouring. The leather is dried and finished under mild conditions. A leather with a dark yellow-brown shade and good fastness properties is obtained.

The following table contains substituents and diazo components of further trisazo dyes prepared according to the instructions of Example 1, which are in the metal-free form of the formula

v ■ ■

009848/1826

OH

N = N-

N = N-E

correspond. In the last five columns of the table the shades of the dyeings on leather are of the metal-free ones Trisazo dyes and indicated by the corresponding copper, cobalt, chromium and iron complexes.

009848/182

Tabel

E.g.

No.

A ¹

H ₂ ND

1. Diazo component

E-NH,

2. Diazo component shade of the dyeing on leather of the metal-free one or metal-containing dyes

metal free

copper

cobalt

chrome

iron

OH

NH.

NH,

OH

NH,

NH,

H.

H,

SO, H

OH

NH.

OH

OH

SO ₃ H

NO,

HO ^ S

Cl

red-brown

Cl

COOH

NH,

SO H

HO'S 3

COOH -Ö-NH.

red-brown

do

do

do

do

red-brown

do

do

do

do

purple brown

do

do

do

do

yellow-brown

do

do

do

do

O O co

OO OO

OO ro CD

E.g. OH A * HgN-D E-NH ₂ Nuance of coloring on leather of the metal-free
or metal-containing dyes copper - do cobalt chrome iron No. 1. Diazo Compo
nent £. Diazo composite
• nente free OH SO-H red-brown red-brown purple brown yellow-brown 7th OH K ₂ NQ-CH ₃ HO ₃ S - (^ - NH ₂ red-brown do SO H COOH
Q-NH ₂ . do do do δ OH OH H ₂ NQ-NO ₂ . 'do do SO ₃ H ' do OH OCH, HO ₃ SQ-NH ₂ do do do 9 OH OH SO, H do .. SO-H Cr ^m z do. do do ίο OH H ₂ NQ-CH ₃ x ^f · ■ do violet
Brown do O
ho
durikel-o
brown j> « 11 OH SO-, Η do

OV

L. Diazo component

2. Diazo component shade of dyeing on leather of the metal-free one or metal-containing dyes'

metal free

copper

cobalt

chrome

iron

Cl

OH

OH

OOH red-brown

red-brown

SO ₃ H

OH

OH

SO ₃ H

COOH

OH

OH

E ^ NONH-O-OGH H

SO_H

OH

OH

H ₀ NQ-NH-OOH SOYH

O ₂ NQ-NH ₂ SO ₃ H

OH

OH

HpN-Q-NH-O SO-Ji

do

do

do

do

violet
Brown

do

purple brown

do

do

do

do

do

do

do

dark brown

do

do

do

do

φ φ

CO

CP

E.g. A. A ¹ HgN-D E-NH ₂ Color shade on the leather of the metal
free or metal-containing dyes metal
free • copper cobalt ■ chrome iron No. 1. Diazo Compo
nent 2. Diazo Compo
nent red-brown red-brown violet
Brown purple brown dark
Brown 17th OH OH SO H SO, H do do red-brown red-brown yellowish brown 18th NHg OH HgN-Q-SO ₅ H O- ^NH 2 CH ■ ^CH 3 do do do do do 19th OH OH H ₂ NO-SO ₃ B HO ₅ SQ-NH ₂ OH SO ₅ H do do do do do 20th OH OH HgN-Q- ³⁰ ^ H ₅ CQ-NH ₂ Cl So\ H ₅ CQ-NH ₂
SO ₃ H do do do do do ZL OH OH H ₂ NT ^ -Br SO ₃ H

00

TO O

CD

O O co OO • Ρ-OO

CO

E.g
No A. A ^! H ₂ ND
1. Diazo Compo
nent 0 E-NHg
• 2. Diazokom
component nuance
freer
metal- ϊ. the Farbui
1 or meta]
copper ig on Lee
Llhal tiger
cobalt ler the metal
1 dyes
chrome iron SO-H t
SO, H
SO H SO H 22nd OH OH H ₃ C - ^ - NH ₂ red-brown red-brown violet
Brown purple brown dark- ,
Brown 23 OH OH
* SO ₃ K
HgN-Q-OCgH ₅ O ₂ N - ^ - NH ₂ do do do do do 24 OH OH SO H SO-H
H, COQ-NH do do red-brown red-brown yellow-brown 25th OH OH H ₁₅ NO-NH-O-CH,
* 'r Γ 3
SO-H NO- SO, H
Q-NH ₂ do do do do do OCH
OCH ₃ 26th OH OH ^ ^NH2 do do riolet
Down there purple brown dark
Brown
1

H VO

TO

O ΓΌ

E.g.

No.

A ¹

H ₂ ND

1. Diazo component

E-NH ₂

2. Diazo component shade of dyeing on leather, metal-free or metal-containing dyes

metal free

copper

cobalt

chrome

iron

27

OH

OH

28

OH

OH

NO,

SO H

-NH ₂

Cl

SO, H NH,

-Q- Cl red-brown

red-brown

do

violet brown

red-brown

purple brown

red-brown

dark brown

yellow-brown

Claims (17)

Claims 1. Polyazo dyes and their metal complex compounds as well Mixtures of such metal complex compounds in the metal-free form of the formula OH A X CD correspond, wherein A and A ¹ stand for an amino or hydroxyl group and X is hydrogen, hydroxyl, halogen, nitro, optionally substituted alkyl or alkoxy or the sulfonic acid group, Y is hydrogen, hydroxyl, halogen, nitro, optionally substituted alkyl or alkoxy. Or the Group . G Π: "'B / 1 8 2 6 where Z is hydrogen, the carboxyl or the sulfonic acid regruppe,
Z ₁ for hydrogen, hydroxyl, nitro _r optionally substituted alkyl or alkoxy and Z _{2 represents} hydrogen or nitro, T is the carboxyl or sulfonic acid group, T, hydrogen, nitro, halogen, optionally substituted alkyl or alkoxy or the sulfonic acid group
and T _n , hydrogen, nitro, halogen or optionally substituted alkyl or alkoxy, and the rings B and / or D contain a sulfonic acid group. 2. The copper complex compounds of the polyazo dyes according to Claim 1. 3 · The cobalt complex compounds of the polyazo dyes according to Claim 1. 4. The chromium complex compounds of the polyazo dyes according to Claim 1. 009848/1826 5. The iron coraplex compounds of polyazo dyes like According to claim 1. · 6. Polyazo dyes and their metal complex compounds ge raäss claim 1, which is in the metal-free form of the Formula ■ - OH OH X N = N- '~ ^l \ IX T. correspond. 7. Polyazo dyes and their metal complex compounds according to Claim 1, which is in the metal-free form of the formula " correspond, 009848/182 6 wherein R is hydrogen, halogen, nitro or low molecular weight Alkyl or alkoxy, R -SO-H or -COOH and R is hydrogen, halogen, nitro or low molecular weight alkyl or alkoxy, 8. Polyazo dyes and their metal complex compounds according to Claim 1, which is in the metal-free form of the formula OH OH SO, H JlP 0 Nf ^v VN = N-fVN = N- / ~> (VIII) I '/ -V ^R 1 NO ₀ N = NC ) wherein R is -SO ₇ H or -COOH and correspond,
-S mean low molecular weight alkoxy. 9. Polyazo dyes and their metal complex compounds according to claim 1, which are in the metal-free form of the formula 009848/182 6. OH correspond to, ■ wherein R _{1 is} -SO_H or -COOH, - | R is hydrogen, halogen, nitro or low molecular weight Alkyl or alkoxy, R. Hydrogen, nitro or -COOH and R ₁ . Hydrogen or nitro mean =. 5 10. Polyazo dyes and their metal complex compounds according to Claim 1, which is in the metal-free form of the formula OH OH S0, H Ks ^{1 1} S ^ A ... "" ^ ^ NO. (X) ΤΌΗ " ^V 2 NO ₂ N = N correspond to ^ wherein R «is -SO ^ H or -COOH. 009848/1826 11. Process for the preparation of polyazo dyes and their metal complex compounds according to claim 1, the in the metal-free form of the formula (i), characterized in that 1 mol of a diazo compound from an amine of the formula NH _o - <bV '(II) with 1 mole of a coupling component of the formula OH O ₂ N to the disazo dye of the formula OH A X couples and this with a diazo compound from an amine of the formula 009848/18 2 8 (ν) converts, and the dyes obtained in this way, if appropriate treated with metal-donating agents in such a way that metal-containing trisazo dyes are formed. 12. The method according to claim 11 for the production of metal-containing compounds, characterized in that the polyazo dyes of the formula (I) in substance or treated on the fiber with metal donors. 13. The method according to claim 11 for the production of metal-containing compounds, characterized in that a metal-containing compound of the formula (III) is used. 14. The method according to claim 11 for the production of metal-containing compounds, characterized in that mixtures of polyazo dyes of the formula (I) in Substance or treated on the fiber with metal donating agents. 15 Process for dyeing leather, characterized in that that one polyazo dyes of the formula (i) and their metal " complex compounds according to claim 1 used. Q09 848/1826 16. Process for dyeing, padding and printing animals and synthetic polyamide fibers, characterized in that polyazo dyes of the formula (I) and their metal complex compounds according to claim 1 are used. 17. The leather dyed according to claim 15. 18, according to claim l6 colored, padded and printed animal and synthetic polyamide fibers, The patent attorney (Dr. V. Schmied-Kowarzik) 009848/1826